Radiation synthesis of PVP/CMC hydrogels as wound dressing

Carboxymethyl cellulose (CMC) and poly(N-vinyl pyrrolidone) (PVP) were blended to synthesize hydrogels by ⁶⁰Co γ-ray irradiation. A series of hydrogels were prepared with three compositions, i.e. PVP:CMC = 5:5, 6:4 and 7:3. The properties of the hydrogels such as gel fraction, gel strength, swelling behavior and moisture retention were investigated. Compared with pure PVP and CMC hydrogels, PVP/CMC blend hydrogels possessed improved gel strength, flexibility and transparency. As the content of PVP in PVP/CMC blend hydrogels increased, the gel fraction increased while the swelling rate decreased. The hydrogels with optimal properties were obtained in a composition of PVP/CMC = 6/4 with sterilization dose (25 kGy) and further characterized by FT-IR and SEM. Properties concerning the application of wound dressing were performed by comparison with a commercial hydrogel wound dressing to find a similar moisture retention capability and improved swelling rate. The improved properties as well as the cheapness of the materials suggest that PVP/CMC blend hydrogel can be good candidate as wound dressing.     

PVA/PVP/ws-chitosan水凝胶伤口敷料的辐射制备及性能表征

采用γ射线辐射法制备了聚乙烯醇(PVA)/聚乙烯基吡咯烷酮(PVP)脉溶性壳聚糖(ws-chitosan)共混水凝胶.研究了辐射剂量、ws-chitosan含量及增塑剂(聚乙二醇(PEG)或甘油)对水凝胶性能的影响.实验发现,随着辐射剂量的增大,凝胶分数增大,并在剂量大于27 kGy时达到饱和;ws-chitosan含量增大及加入增塑剂PEG或甘油后,水凝胶的凝胶分数和强度都会减小,而相应的溶胀度会显著增大.通过高级流变仪(ARES)对水凝胶弹性模量的测试显示,随吸收剂量的增加,凝胶强度会相应增大,但在27 kGy以上出现饱和.     

Chemical and physical properties of poly（vinyl alcohol）hydrogel films formed by irradiation

Chemical and physical properties of poly(vinyl alcohol)(PVA) hydrogel films were investigated as a function of production factors.The experimental results show that the gel fraction depends strongly on the radiation dose.the degree of swelling is inversely dependent on the concentration of PVA solution,the tensile strength depends mainly on the PVA blending ration and the elongation at break is inversely dependent on the radiation dose.     

聚氧化乙烯水凝胶膜的辐射接技研究(英)

为了得到一种理想的水凝胶伤口敷料,研究了应用电子束辐射接枝了不同比例聚乙烯醇（PVA）的聚氧化乙烯（PEO）水凝胶膜的制备和该膜的理化特性。实验结果显示,PEO接枝水凝胶膜的凝胶分数主要依赖于辐射剂量和聚合物浓度。而其溶胀度与辐射剂量聚合物的浓度;混合比例和分子量密切相关。该膜的抗张强度和断裂伸长率则明显地依赖于辐射剂量和聚合物的混合比例。实验发现,比例为7：3的20wt％PEOE-30接枝水凝胶膜与其它PEO接枝水凝胶膜和单纯PEOE-30水凝胶膜相比具有较好的理化特性,例如韧性,较少气泡,适度的凝胶分数,溶胀度和断裂伸长率,尤其它的较高的抗张强度。实验结果表明,PVA在辐射接枝后能够通过降低PEO水凝胶膜的溶胀度而改善PEO水凝胶膜的机械强度。     

PVA/PEO/Chitosan水凝胶膜的辐照法制备及其性能研究

研究了辐照剂量和壳聚糖含量对水凝胶膜性能的影响。以聚乙烯醇(PVA)、聚氧化乙烯(PEO)和壳聚糖(Chitosan)为原料,采用γ射线辐照法制备了一种新型水凝胶膜。结果表明,随着辐照剂量的增大,凝胶分数会增大,溶胀率会降低;辐照剂量达到21kGy时,凝胶分数可以达到70%,辐照剂量大于21kGy以后,拉伸强度和断裂伸长率会随着辐照剂量的增大而降低;随着壳聚糖含量的增加,水凝胶膜的凝胶分数、拉伸强度和断裂伸长率都会减小,而溶胀率会有一定的提高。辐照后壳聚糖的一些特殊官能团没有改变,将会保持它的抑菌性能,从而获得了一种新型水凝胶膜。     

聚乙烯醇水溶液的辐射效应及某些添加剂的影响

测定了几种浓度的聚乙烯醇（ＰＶＡ）水溶液辐照后的凝胶含量，随着吸收剂量的增大，凝胶含量增加，同一吸收测量下，随着ＰＶＡ浓度的增加，其凝胶含量先上升后趋于饱和，三聚氰酸，Ｎ，Ｎ′－亚甲基双丙烯酰胺和和六次甲基四胺等对ＰＶＡ水溶液的辐射交联有敏化作用，可使凝胶剂量降低。样品的电镜图也表明加入添加剂的ＰＶＡ水凝胶结构的差异。还测定了水凝胶的含水量与浸泡时间的关系及水凝胶的饱和含水量与吸收剂量的关系。     

Vitamin C hinders radiation cross-linking in aqueous poly(vinyl alcohol) solutions

Poly(vinyl alcohol) (PVA) is a promising semi-crystalline material for biomedical applications. It is soluble in water and can be formed into hydrogels by freezing and thawing or crystallizing from an aqueous theta solution such as that of polyethylene glycol (PEG). Radiation cross-linking caused by sterilization or high dose irradiation of concentrated PVA solutions could compromise some properties of these hydrogels. Therefore, we hypothesized that radiation cross-linking of PVA solutions and PVA-PEG theta gels could be prevented by using the antioxidant vitamin C as an anticross-linking agent. Our hypothesis tested positive. Vitamin C concentrations of 0.75 and 4.5 mol/mol of PVA repeating unit could prevent cross-linking in 17.5 wt/v% PVA solutions made with PVA molecular weight of 115,000 g/mol irradiated to 25 and 100 kGy, respectively. Vitamin C also prevented cross-linking in 25 kGy irradiated PVA-PEG theta gels containing up to 5 wt% PEG and decreased the viscosity of those up to 39 wt%.     

Enhancement of the electrical performance of poly(vinyl) alcohol by doping with chlorophyll and gamma irradiation

The electrical properties of poly(vinyl) alcohol (PVA) have been improved pronouncedly by doping with chlorophyll (Chl) and gamma irradiation. PVA/Chl films have been prepared and irradiated with γ-rays at dose levels of 10, 20, 30, 50, 70, 100, 150, 200 and 250 kGy. The crystalline and chemical structures of the samples have been studied using XRD and FTIR techniques. Also, the direct current electrical conductivity and the dielectric constant and loss have been determined for the proposed samples before and after gamma exposure. It is clearly shown that the electrical conductivity of PVA films was increased two orders of magnitude due to chlorophyll doping and about fifteen times due to gamma irradiation. Considering the dielectric constant and loss, their values were shown to increase significantly due to PVA doping with chlorophyll. The obtained results can be attributed to the existence of the conducting Mg atom, as well as, the conjugated double bonds in the chlorophyll. Moreover, the gamma irradiation of PVA/Chl, over 50 kGy, improves also this electrical performance. Therefore, the study suggests the possibility of the utilization of the gamma irradiated PVA/Chl films in different electronic applications.     

Radiation-chemical synthesis of poly(vinyl alcohol) hydrogel containing dicyclohexano-18-crown-6

Radiation-chemical synthesis of poly(vinyl alcohol) hydrogels containing physically immobilized dicyclohexano-18-crown-6 was carried out. Remarkable gel fraction of 40-70% was observed at absorbed dose of about 5 kGy. Increasing degree of poly(vinyl alcohol) crosslinking led to growth of the efficiency of crown ether immobilization. Post-irradiation thermal annealing of the hydrogel samples at 120 °C for 0.5-5 h resulted in an increase of crown ether retention as compared with non-annealed samples by approximately 20% at the same absorbed dose. Preliminary results on a sorption behavior of the crown-containing hydrogels with respect to Sr²⁺ cations in 2.4 M HNO₃ solution are presented.     

PEO/PVA水凝胶伤口敷料的毒性和疗效评价

为了证价经冻融循环处理和电子束辐射交联接技术术合成的聚氧化乙烯与聚乙烯醇（ＰＥＯ／ＰＶＡ）混合物水凝胶伤口敷料的性能,研究了该水凝胶膜对机体和细胞的毒性以及对皮肤伤口的愈合作用。毒性作用通过仇性全身毒性试验、细胞毒性试验和皮肤斑贴试验检测。细胞毒性试验应用高敏感性的成纤维细胞持续培养７ｄ的ＲＰＭＩ－１６４０２培养系统,检测细胞生长抑制和镜下细胞形态学变化。结果显示,ＰＥＯ／ＰＶＡ水凝胶敷料没有引起     

含药聚氧化乙烯共聚水凝胶膜的制备及其性能研究

应用冻融循环和辐射交联技术,制备了含有醋酸氨苄磺胺的的聚氧化乙烯共聚水凝胶膜,并对其理化性能和药物释放进行了研究。实验结果显示,与未经冻融循环处理的聚氧化乙烯共聚水凝胶膜比较,增强的了矣氧化乙烯共聚水凝胶膜抗强度明显增加（Ｐ〈０．０１）,凝胶分数和断裂伸长率亦稍有增加,表明冻融循环处理可明显地改善该膜的机械性能,使该膜作为伤口敷料具有理想的柔韧性、交联度和伸缩性。溶用蔗研究显示,该水凝胶膜的平衡水     

乙烯-乙烯醇共聚物(EVOH)的辐射效应研究

用凝胶抽提、凝胶渗透色谱以及傅立叶变换红外光谱等方法研究了两种乙烯-乙烯醇共聚物（Ethylene-vinyl alcohol copolymers,EVOH）本体和E151／甘油体系的室温辐射效应。在氮气保护下,试样在^60Co源中的吸收剂量最高达到1800kGy。结果显示,EVOH在室温下是一种十分难交联的聚合物。E151本体（乙烯醇摩尔分数56％）在吸收剂量达到800kGy时出现痕量凝胶,当吸收剂量增至1200kGy时,体系凝胶含量也只有5．9％。而F101本体（乙烯醇摩尔分数68％）在1800kGy才出现痕量凝胶。造成这两种EVOH的凝胶化剂量不同的原因是乙烯醇基含量不同。EVOH在辐照过程会产生共轭双键,其含量在辐照初期随吸收剂量的增加而增大,达到最大值后随吸收剂量的增加而减少。双键的存在促使EVOH产生了交联。加入增塑剂甘油后,体系在800kGy以前与本体一样无凝胶,而在800kGy之后凝胶含量随着吸收剂量的增大而增大,且比本体E151的凝胶含量值大。     

电子辐照PVA/CMC共混水凝胶的成胶研究

本试验利用电子辐照PVA/CMC共混水凝胶,通过外观透明度、凝胶分数、溶胀度和红外光谱分析,研究了样品中结构的变化与外观透明度、凝胶分数和溶胀度的关系,以及辐照剂量对样品中结构和性能的影响.结果表明,不同比例的PVA与相同比例的CMC组成的共混水凝胶,经电子辐照后呈现不同的宏观特性.辐照样品萃取后得到的凝胶比萃取前的混合凝胶拥有更强的吸水性,表明辐照PVA/CMC共混凝胶形成了网状结构凝胶.几种竞争反应导致不同辐照剂量下混合凝胶中凝胶含量随PVA含量的变化变得复杂.辐照后样品的红外光谱分析显示,辐照使凝胶中部分仲醇中C上链接的H原子被取代而转变为叔醇,从而产生交联.     

辐射合成法合成明胶类水凝胶及其性能研究

采用辐射法合成了明胶/羧甲基纤维素钠（CMC-Na）/聚乙烯吡咯烷酮（PVP）水凝胶,利用索氏提取器、紫外-可见分光光度计以及原子光谱仪分别对其溶胀性、pH值敏感性、凝胶含量及其对Cr（Ⅵ）的吸附性能进行了测试分析。在剂量率约为83 Gy/min,吸收剂量为15、25、35和45 kGy条件下,明胶/CMC-Na/PVP质量比为4∶1∶2、4∶1∶5和2∶1∶5的明胶/CMC-Na/PVP水溶液经辐照均能交联合成水凝胶。在高纯水中,该类水凝胶溶胀率分布于11～56之间;在pH=1的高氯酸溶液中,所有凝胶的溶胀率较之水溶液中均有所下降,说明这类水凝胶对pH值敏感。不同原料比例生成的水凝胶,其溶胀率并未随吸收剂量的增大而呈现出明显的增加。比例为4∶1∶5的水凝胶溶胀性能最为优良,其溶胀率最大值为56。合成的明胶/CMC-Na/PVP水凝胶可在1个月内完全腐化分解,说明在PVP中添加明胶和CMC-Na后,引入了天然高分子材料优良的降解性能,加速了凝胶分解,缩短了降解时间。同时,发现该类凝胶具有极强的吸Cr（Ⅵ）能力,可达0.539 g/g。     

含冠醚基团水凝胶的辐射制备及其对锂离子的响应性能

利用?射线辐照引发含双键的丙烯酸12冠4醚酯(V12C4)与丙烯酰胺(AM)发生共聚和交联反应,制备了新型的聚丙烯酰胺-丙烯酸12冠4醚酯(PAM-12C4)水凝胶。采用凝胶分析,显微红外,热重分析对PAM-12C4进行表征,并考察了PAM-12C4对水溶液中Li+的溶胀度响应性。研究表明,γ射线辐照可成功引发V12C4与AM发生共聚及交联反应,辐照至吸收剂量10 k Gy时得到PAM-12C4的凝胶分数为94%。该新型含冠醚基团的水凝胶具有良好的热稳定性,在水溶液中对Li+具有明显的选择性溶胀度响应。     

Fabrication of stable MWCNT bucky paper for solar-driven interfacial evaporation by coupling y-ray irradiation with borate crosslinking

Herein,we report a facile solution process for preparing multi-walled carbon nanotube(MWCNT)bucky paper for solar-driven interfacial water evaporation.This process involves vacuum filtrating a dispersion of MWCNTs that was modified by polyvinyl alcohol(PVA)under γ-ray irradiation on a cellulose acetate microporous membrane,followed by borate crosslinking.Fourier transform infrared spectroscopy,Raman spectroscopy,and thermogravimetry confirmed the success of PVA grafting onto MWCNTs and borate crosslinking between modified MWCNT nanoyarns.The as-prepared crosslinked MWCNT bucky papers(BBP membranes)were used as a solar absorber,by placing them on a paper-wrapped float-ing platform,for interfacial water evaporation under simulated solar irradiation.The BBP membranes showed good water tolerance and mechanical stability,with an evaporation rate of 0.79 kg m-2 h-1 and an evaporation efficiency of 56％under 1 sun illumination in deionized water.Additionally,the BBP membranes achieved an evaporation rate of 0.76 kg m-2 h-1 in both NaCl solution(3.5 wt％)and sulfuric acid solution(1 mol L-1),demon-strating their impressive applicability for water reclamation from brine and acidic conditions.An evaporation rate of 0.70 kg m-2 h-1(very close to that from deionized water)was obtained from the solar evaporation of saturated NaCl solution,and the BBP membrane exhibited unexpected stability without the inference of salt accumulation on the membrane surface during long-term continuous solar evaporation.     

Effect of ion and electron beam irradiation on surface morphology and optical properties of PVA

Polyvinyl alcohol(PVA) is a well-known friendly polymer for paper-making, textiles, and a variety of coatings, biomedical applications such as artificial pancreas, synthetic vitreous body, wound dressing, artificial skin,and cardiovascular device. In this paper, ion/electron beam is employed to get insight into the irradiation effect on surface morphology and optical properties of PVA polymer. UV-Vis spectra are recorded to investigate the effect of induced defects on the optical band gap and the formed carbon clusters size. Scanning electron microscopy(SEM) is used to relate and investigate surface morphology and optical properties of the target polymer with different doses(15, 30 and 60 min). Also, PVA polymer is subjected to theoretical studies by using semi-empirical PM7 quantum chemical method.     

Removal of Co2+ from radioactive wastewater by polyvinyl alcohol (PVA)/chitosan magnetic composite

Cobalt is one of the toxic radioactive elements and the removal of Co²⁺ from radioactive wastewater has received increasing attention in recent years. In this paper, polyvinyl alcohol (PVA)/chitosan magnetic composite was prepared and used for Co²⁺ removal. The effect of initial pH, contact time and initial Co²⁺ concentration on Co²⁺ adsorption was investigated. The kinetics, thermodynamic and isotherms of Co²⁺ sorption onto the composite were determined. The results showed that pseudo second-order equation could be used to describe the Co²⁺ removal process. The maximum sorption capacity was calculated to be 14.39 mg/g at pH 6.0 and 30 °C using the Langmuir model. The analysis of FTIR and SEM-EDAX were performed before and after Co²⁺ sorption onto the PVA/chitosan magnetic beads, revealing that the functional groups –NH₂ and –OH played main role in Co²⁺ sorption process. PVA/chitosan magnetic composite is promising adsorbent for removing Co²⁺ radioactive wastewater.     

Use of poly(methyl methacrylate) in radioactive waste management: I. Radiation stability and degradation

In this study, in order to understand the possible use of PMMA in radioactive waste management as a solidifying agent, radiation stability of the PMMA was studied by gamma irradiations at two different dose rates of 1485 and 82.8 Gy/h. The total dose of irradiation was up to 523 kGy. Degradation nature was tested by studying the changes in mechanical and thermal properties with rate and total dose of irradiation. Ultimate tensile strength and toughness first increased and then decreased with total irradiation dose. Half value dose (HVD) for elongation was 148 kGy and it was 178 kGy for tensile strength at the dose rate of 1485 Gy/h. Half value dose was found from the extrapolation of experimental data as 228 kGy for elongation and 205 kGy for tensile strength at the dose rate of 82.8 Gy/h. The FTIR spectral analysis showed depolymerization degradation of polymer with irradiation. It was concluded from experimental results that PMMA can be used for embedding radioactive wastes.     

稳定剂对PVC辐射变色性能影响的研究

采用^60Coγ射线对聚氯乙烯（Polyvinyl chloride,PVC）／稳定剂复合体系进行辐照。研究了不同稳定剂对PVC辐射变色．陛能的影响;并采用紫外光谱仪（Ultraviolet spectrometer,UV）和傅立叶变换红外光谱仪（Fouriertransform infrared spectrometer,FT—IR）对其结构进行了表征。结果表明,硬脂酸钙（Calcium stearate,CaSt）,硬脂酸锌（Zinc stearate,ZnSt）复合稳定剂、环氧大豆油、亚磷酸酯和光稳定剂的加入可提高PVC耐辐射变色性能。亚磷酸酯的加入可提高PVC的耐辐射氧化性能。在相同吸收剂量下,添加硬脂酸钙／硬脂酸锌复合稳定剂的PVC具有优异的耐辐射变色性能。在吸收剂量为30kGy时,CaSt：Znst为4：1的PVC黄变指数变化率为8．3％。PVC经辐照后主要形成3至4个共轭双键的不饱和酮或共轭烯烃结构。